Polymers of macrocyclic metal chelators and methods for the preparation and use thereof

Abstract

Polymers and copolymers are derived from substituted macrocyclic metal chelators. These polymers may be cross-linked, and are typically insoluble in most solvents. The metal complexes of these polymers exhibit the useful catalytic activity of the monomers. The polymers are advantageously prepared by reacting a polybasic nucleophile with the substituted macrocyclic metal chelator. Copolymers of the macrocyclic metal chelators with other polyfunctional monomers are also formed by reaction with suitable polybasic nucleophiles. Suitable macrocyclic metal chelators for use as monomers in accordance with the present invention have at least one leaving group substituent which is labile for aromatic nucleophilic substitution and at least one electronegative (or electron-withdrawing) substituent.

What is claimed is: 
     
       1. A polymer comprising at least one macrocyclic metal chelator as a repeating monomeric unit, said macrocyclic metal chelator monomeric unit being derived from a monomer containing at least one leaving group substituent which is labile for aromatic nucleophilic substitution and at least one electronegative substituent. 
     
     
       2. A polymer according to claim 1, wherein said polymer comprises the reaction product of said monomer and a polybasic nucleophile, such whereby the at least one leaving group on the monomer is replaced by the nucleophile to form a bridging group. 
     
     
       3. A polymer according to claim 1, further comprising at least one metal complexed with said macrocyclic metal chelator. 
     
     
       4. A polymer according to claim 1, wherein said at least one macrocyclic metal chelator is selected from the group consisting of porphyrins, benzporphyrins, phthalocyanines, porphycenes, oxaporphycenes, cryptands, sappharins and crown ethers. 
     
     
       5. A polymer according to claim 1, wherein said monomer has the Formula I ##STR10## wherein each X is independently selected from the group consisting of leaving groups labile to aromatic nucleophilic substitution, electronegative substituents, non-interfering substituents and R; each Y is independently selected from the group consisting of leaving groups labile to aromatic nucleophilic substitution, electronegative substituents, non-interfering substituents and R; and   R is aryl which is fully substituted by Z groups, in which each Z is independently selected from the group consisting of leaving groups amenable to aromatic nucleophilic substitution, electronegative substituents and non-interfering substituents, with the proviso that at least one X, Y or Z substituent is a leaving group and at least one other X, Y or Z substituent is an electronegative group.     
     
     
       6. A polymer according to claim 1, wherein the monomer has the Formula III ##STR11## in which each X 1  is independently selected from the group consisting of leaving groups labile to aromatic nucleophilic substitution, electronegative substituents, non-interfering substituents and R 1  ; B is ═N-- or ═CY 1  --, in which each Y 1  is independently selected from the group consisting of electronegative substituents and non-interfering substituents; and   R 1  is aryl which is fully substituted by Z 1 , in which each Z 1  is independently selected from the group consisting of leaving groups amenable to aromatic nucleophilic substitution, electronegative substituents and non-interfering substituents, with the proviso that at least one X 1  or Z 1  substituent is a leaving group and at least one other X 1  or Z 1  substituent is an electronegative group.     
     
     
       7. A polymer according to claim 1, wherein the monomer has the Formula IV ##STR12## wherein each X is independently selected from the group consisting of leaving groups labile to aromatic nucleophilic substitution, electronegative substituents, non-interfering substituents and R; each Y is independently selected from the group consisting of leaving groups labile to aromatic nucleophilic substitution, electronegative substituents, non-interfering substituents and R; and   R is aryl which is fully substituted by Z groups, in which each Z is independently selected from the group consisting of leaving groups amenable to aromatic nucleophilic substitution, electronegative substituents and non-interfering substituents, with the proviso that at least one X, Y or Z substituent is a leaving group and at least one other X, Y or Z substituent is an electronegative group; and     B 4  is N-H and B 4'  is N or B 4  is O and B 4'   is O + .   
     
     
       8. A polymer according to claim 1, wherein the monomer has the Formula V ##STR13## wherein each X is independently selected from the group consisting of leaving groups labile to aromatic nucleophilic substitution, electronegative substituents, non-interfering substituents and R; each Y is independently selected from the group consisting of leaving groups labile to aromatic nucleophilic substitution, electronegative substituents, non-interfering substituents and R; and   R is aryl which is fully substituted by Z groups, in which each Z is independently selected from the group consisting of leaving groups amenable to aromatic nucleophilic substitution, electronegative substituents and non-interfering substituents, with the proviso that at least one X, Y or Z substituent is a leaving group and at least one other X, Y or Z substituent is an electronegative group.     
     
     
       9. A polymer according to claim 1, wherein the monomer has the Formula VI ##STR14## in which each B independently selected from the group consisting of --S--, --O-- and --NY 6  ; and each X 6  is independently selected from the group consisting of leaving groups labile to aromatic nucleophilic substitution, electronegative substituents, non-interfering substituents and R 6  ;   each Y 6  is independently selected from the group consisting of electronegative substituents and non-interfering substituents; and   R 6  is aryl which is fully substituted by Z 6 , in which each Z 6  is independently selected from the group consisting of leaving groups amenable to aromatic nucleophilic substitution, electronegative substituents and non-interfering substituents, with the proviso that at least one X 6  or Z 6  substituent is a leaving group and at least one other X 6  or Z 6  substituent is an electronegative group.     
     
     
       10. A polymer according to claim 1, further comprising at least one additional repeating monomeric unit derived from a compound of Formula IX   (A)--(R.sup.11 X.sup.11).sub.n,     wherein the --R 11  X 11  substituents are the same or different and in which n is an integer >2;   A is a direct bond (when n═2), a bridging atom or a bridging group;   R 11  is an unsubstituted or substituted alkylene or arylene moiety; and   X 11  is a leaving group amenable to nucleophilic substitution.   
     
     
       11. A polymer according to claim 1, wherein the monomer is selected from the group consisting of crown ethers and derivatives of crown ethers in which at least one O is replaced by one of --S--, --NY 10  and mixtures thereof, in which each Y 10  is independently selected from the group consisting of non-interfering substituents. 
     
     
       12. A polymer comprising the reaction product of at least one polybasic nucleophile and at least one macrocyclic metal chelator monomer containing at least one leaving group substituent which is labile for aromatic nucleophilic substitution and at least one electronegative substituent. 
     
     
       13. A polymer according to claim 12, wherein the polymer is the reaction product of said at least one nucleophile, said at least one macrocyclic metal chelator and a further monomer of Formula XI   (A)--(R.sup.11 X.sup.11).sub.n,     wherein the --R 11  X 11  substituents are the same or different and in which n is an integer ≧2;   A is a direct bond (when n═2), a bridging atom or a bridging group;   R 11  is an unsubstituted or substituted alkylene or arylene moiety; and   X 11  is a leaving group amenable to nucleophilic substitution.   
     
     
       14. A method of preparing a polymer comprising at least one macrocyclic metal chelator as a repeating monomeric unit, said method comprising: reacting at least one polybasic nucleophile with at least one macrocyclic metal chelator monomer containing at least one leaving group substituent which is labile for aromatic nucleophilic substitution and at least one electronegative substituent; and   recovering the resultant reaction product.   
     
     
       15. A method according to claim 14 wherein said at least one polybasic nucleophile and said at least one macrocyclic metal chelator monomer are reacted with a further co-monomer of Formula XI   (A)--(R.sup.11 X.sup.11).sub.n,     wherein the --R 11  X 11  substituents are the same or different and in which n is an integer ≧2;   A is a direct bond (when n═2), a bridging atom or a bridging group;   R 11  is an unsubstituted or substituted alkylene or arylene moiety; and   X 11  is a leaving group amenable to nucleophilic substitution.   
     
     
       16. A method according to claim 14, wherein said polybasic nucleophile is selected from the group consisting of dianions, alkoxides, mercaptides, amines and amides.